CN109012224A - The method that a kind of nanometer of confinement growth in situ prepares ZIF-8@graphene oxide hybridized film - Google Patents

The method that a kind of nanometer of confinement growth in situ prepares ZIF-8@graphene oxide hybridized film Download PDF

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CN109012224A
CN109012224A CN201811076622.7A CN201811076622A CN109012224A CN 109012224 A CN109012224 A CN 109012224A CN 201811076622 A CN201811076622 A CN 201811076622A CN 109012224 A CN109012224 A CN 109012224A
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安全福
张文海
金成刚
王乃鑫
纪树兰
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Beijing University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/027—Nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/02—Inorganic material
    • B01D71/021—Carbon
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/10—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/308—Dyes; Colorants; Fluorescent agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen

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Abstract

The method that a kind of nanometer of confinement growth in situ prepares ZIF-8@graphene oxide hybridized film, belongs to UF membrane field.It mainly comprises the steps that and porous basement membrane is pre-processed, remove its surface organic matter, inorganic matter and microorganism；In deionized water by the dispersion of GO powder, in the way of ultrasound centrifugation, GO dispersion liquid is configured；By the way of filtering deposition, GO is assembled to porous membrane surface, prepares the GO composite membrane of hygrometric state；Resulting hygrometric state GO composite membrane is prepared to the GO composite membrane of open structure using Freeze Drying Technique；Zinc nitrate hexahydrate and 2-methylimidazole are configured to ZIF-8 precursor solution；Precursor solution is filled in film and surface, and uses lye nucleation and crystallization, constructs ZIF-8@f-GO hybridized film.For dyestuff, high price salt, the separation of organic system small molecular and gas separation in water, there is good separation property and stability.

Description

The method that a kind of nanometer of confinement growth in situ prepares ZIF-8@graphene oxide hybridized film
Technical field
The present invention relates to the methods that nanometer confinement growth in situ prepares ZIF-8@graphene oxide hybridized film, belong to UF membrane Field.
Background technique
Graphene oxide (GO) as the oxidized derivatives of graphene not only maintain part graphene superior function and It is easy to large scale preparation.In addition, GO can be filtered deposition or spin coating is assembled into and possesses two-dimensional nano duct abundant network Macroscopical membrane material, thus the material separation field have boundless application potential [E.N.Wang and R.Karnik, Nature Nanotechnology.2012,7,552.].It is filtered on porous support membrane by single layer or widow layer GO, with high score Sub- membrane material composite, or can get high-performance seperation film with means such as inorganic material hydridization, it is used for ultrafiltration, nanofiltration, reverse osmosis Thoroughly, just permeate, infiltration evaporation, gas separation etc. a variety of membrane separating process [Liu G, Jin W, Xu N.Chemical Society Reviews,2015,44(15):5016.】。
However, the mass transfer of GO film relies primarily on interlayer two-dimensional channel, since inter-layer passages complications make mass transfer path significantly Extend, reduces infiltration rate, in addition, recent studies have shown that GO film in the process of running, there are microstructure densification to cause to lead to Amount substantially decays and dissociates phenomenon in water, this series of problems greatly limits industrial application [the Wei Y, Zhang of GO film Y,Gao X,et al.Carbon,2016,108:568-575；Chong J Y,Wang B,Mattevi C,et al.Journal of Membrane Science,2017,549.].For this purpose, a series of improved methods are suggested.It is ground at present In studying carefully, the mode for improving GO membrane flux and stability specifically includes that a. is chemically crosslinked, such as selects polyamine, polynary acyl chlorides Molecule is chemically crosslinked with lamella；B, using nano particle filling technique, the building of GO interlayer nanometer mass transfer channel is realized.On Support, firm and regulation interlamellar spacing can be played by stating method.But two ways has itself deficiency, such as small-molecule chemical It is crosslinked little for the contribution for improving permeation flux；The filling hydridization that nano particle (template) is introduced in a manner of physical blending is difficult To realize that controllable building and the particle agglomeration of nanometer transmission channel are easy to lead to the problem of defect and reduce separation selectivity.For This, a kind of method for developing porous material in-situ hybridization is the key that solve the above problems.
Zeolite imidazole ester frame structure material (ZIF-8) is a kind of novel porous metal organic framework developed in the recent period (MOFs) material is widely used in the preparation of seperation film because its special pore structure and performance such as stablize at the features, and have compared with For excellent separating property [CN106823854A, CN105582823A, CN104209021A].However, making currently with ZIF-8 It is mostly direct physical blending to fill the hydridization film-forming method of phase, causes dispersion uneven and be easy to reunite when additive amount is higher. And in-situ hybridization is a kind of very strong solution, however pure GO film is comparatively dense because of interlayer accumulation, it is difficult to it carries out former Position growth, and the premise of in-situ hybridization growth is building particle growth space.
Freeze-drying, also known as ice template technology are that the one kind to grow up in the recent period very effective prepares porous material Method [CN107200583A, CN106084302A, CN107185500A], thus the present invention pass through combine Freeze Drying Technique And the standby zeolite imidazole ester skeleton structure@graphite oxide with controllable split tunnel structure of in-situ hybridization growth pathway coordinate system Alkene hydridization (ZIF-8@f-GO) seperation film, effectively controls split tunnel structure by this method, is applied to different separation systems, and And preparation process is simple, and it is reproducible, there is very big potential application foreground in UF membrane field.
Summary of the invention
The purpose of the present invention is have controllably to separate with the collaboration building of in-situ hybridization growth pathway using Freeze Drying Technique The ZIF-8@f-GO hybridized film of channel design.There is the f-GO composite membrane of nano pore by freeze-drying building, then will ZIF-8 precursor solution is filled in hole, and nucleation and crystallization growth in situ ZIF-8 is finally carried out, which passes through freeze-drying and original Position hybridisation process carries out cooperative achievement.Composite membrane using this method preparation has very for liquid phase nanofiltration and gas separation field Good separating property and stability.
The method that a kind of nanometer of confinement growth in situ prepares ZIF-8@graphene oxide hybridized film, which is characterized in that the party Method the following steps are included:
(1) porous basement membrane is pre-processed, removes its surface organic matter, inorganic matter and microorganism；
(2) in deionized water by the dispersion of GO powder, in the way of ultrasound centrifugation, GO dispersion liquid is configured；
(3) by way of filtering deposition, GO is assembled to porous membrane surface, prepares the GO film of hygrometric state；
(4) GO for the resulting hygrometric state GO composite membrane of step (3) being prepared open structure using Freeze Drying Technique is compound Film (f-GO)；
(5) zinc nitrate hexahydrate and 2-methylimidazole are configured into ZIF-8 precursor solution according to certain mol proportion example；
(6) by the precursor solution prepared in (5) in the GO composite membrane (f-GO) of step (4) resulting open structure and Surface is filled and (different modes, such as dynamic filtration can be used), then the nucleation and crystallization in lye, and building ZIF-8@aoxidizes stone Black alkene (ZIF-8@f-GO) hybridized film.
Be used to prepare in the present invention polyelectrolyte composite membrane substrate can for business tubular membrane or plate membrane it is inorganic Perforated membrane, membrane material are aluminium oxide, silica, zirconium oxide, and the porous membrane aperture is 0.1~1.0 μm；
GO dispersion liquid mass percent concentration in step (2) for assembling is 0.001~0.5%；
The pressure limit that deposition is filtered in step (3) is 0.01~0.1MPa, and deposition time ranges are 0.1~10min；
Freeze Drying Technique in step (4) is that first then Decompression Sublimation is dry for freezing ice crystalization, freezes ice crystallization temperature Be -10~-50 DEG C, freezing ice crystallization time be 0.5~3h, 1~10Pa of pressure of Decompression Sublimation, the lyophilization time be 1~ 10h；
ZIF-8 presoma zinc nitrate hexahydrate is added in step (5) and 2-methylimidazole molar concentration be respectively 0.1~ 10mol/L, two kinds of monomer mole ratios are 10~0.1；One or more of water or organic solvent such as methanol can be used in solvent；
Filling mode is static dipping, filters deposition, vacuum outgas in step (6), and lye nucleating agent is ammonium hydroxide and methanol The volume ratio of mixed solution, ammonium hydroxide and methanol is 100~0:1, and the concentration of ammonium hydroxide used is 30wt%.
Gained film can be respectively used to dyestuff in water, high price salt is separated by filtration, being separated by filtration such as small molecule in organic phase, And gas separation.
The principle of technical solution of the present invention is: preparing the GO composite membrane of hygrometric state first using the method for filtering deposition, and leads to Cross low temperature and carry out freezing processing, when being lower than solvent freezing point, solvent solidifies, generate the solvent nucleus of nano-scale, then into The method of row negative pressure distillation removes solvent and fills ZIF-8 precursor solution to this to construct the space of special microcellular structure Nano-space, and the growth of in-situ crystallization hydridization is carried out in lye.It is controllable that the method constructs a kind of stable structure, separated pore ZIF-8@f-GO hybridized film.
Technical advantage
The present invention constructs the ZIF-8@f-GO hybridized film of controllable split tunnel structure using Freeze Drying Technique, is stablizing GO The theory of split tunnel structure-controllable is realized while membrane structure, to be applied to different separation fields；This method is allusion quotation The in-situ hybridization technology of type, easy to operate and stable structure have commercial introduction potentiality.The ZIF-8@f- prepared using the technology GO hybridized film is for separating such as the methyl blue water solution system of 0.1g/L, the aqueous sodium sulfate liquid system of 1g/L, the first of 0.1g/L Base indigo plant methanol solution system and hydrogen/nitrogen separation, when operating pressure is 0.1MPa, flux may respectively be 50.8L/m2h bar、59.2L/m2h bar、58.6L/m2H bar and 106GPU；Rejection can be followed successively by 99.8%, 68.3%, 91.1%, hydrogen Gas/nitrogen perfect gas is selectively 7.6.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the ZIF-8@f-GO hybridized film section of freeze-drying process in embodiment 1,
Fig. 2 is the scanning electron microscope (SEM) photograph of ZIF-8 f-GO hydridization film surface in embodiment 1.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is described in detail, but the present invention is not limited to following embodiments.
Embodiment 1
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (pressure 1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out and dries, and is subsequently placed in ammonia hydroxide/methanol mixed solution that (volume ratio 1:1, the concentration of ammonium hydroxide used are 30%) crystallization nucleation 12h, final washing, drying.It is molten to aqueous phase system 0.1g/L methyl blue when operating pressure is 0.1MPa Liquid rejection and flux are respectively 99.8% and 31.1L/m2h bar。
Embodiment 2
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation；Final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) f-GOm obtained in step (4) is impregnated in the ZIF-8 presoma methanol solution configured in step (5) 12h takes out and dries, be subsequently placed in ammonia hydroxide/methanol mixed solution (volume ratio 10:1, the concentration of ammonium hydroxide used are 30%, Crystallization nucleation 12h, final washing, drying.When operating pressure is 0.1MPa, aqueous phase system 0.1g/L methyl blue solution is retained Rate and flux are respectively 99.8% and 37.2L/m2h bar。
Embodiment 3
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GOm
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out and dries, and is subsequently placed in ammonia hydroxide/methanol mixed solution that (volume ratio 100:1, the concentration of ammonium hydroxide used are 30%) crystallization nucleation 12h, final washing, drying.It is molten to aqueous phase system 0.1g/L methyl blue when operating pressure is 0.1MPa The rejection and flux of liquid are respectively 99.8% and 40.3L/m2h bar。
Embodiment 4
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out and dries, and is subsequently placed in 12h in methanol, final washing, drying.When operating pressure is 0.1MPa, to water phase System 0.1g/L methyl blue solution rejection and flux are respectively 96.8% and 36.1L/m2h bar。
Embodiment 5
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out drying, and being subsequently placed in ammonia hydroxide/methanol mixed solution, (30%) volume ratio 100:1, the concentration of ammonium hydroxide used are Middle crystallization nucleation 12h, subsequent degassifying using vacuum 30min, final washing, drying.When operating pressure is 0.1MPa, to aqueous phase system The rejection and flux of 0.1g/L methyl blue solution are respectively 99.8% and 50.8L/m2h bar。
Embodiment 6
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out drying, and being subsequently placed in ammonia hydroxide/methanol mixed solution, (30%) volume ratio 100:1, the concentration of ammonium hydroxide used are Middle crystallization nucleation 12h, subsequent degassifying using vacuum 30min, final washing, drying.When operating pressure is 0.1MPa, to aqueous phase system The rejection and flux of 1g/L metabisulfite solution are respectively 68.3% and 59.2L/m2h bar。
Embodiment 7
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.003g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out drying, and being subsequently placed in ammonia hydroxide/methanol mixed solution, (30%) volume ratio 100:1, the concentration of ammonium hydroxide used are Middle crystallization nucleation 12h, subsequent degassifying using vacuum 30min, final washing, drying.When operating pressure is 0.1MPa, to methanol phase body It is the rejection of 0.1g/L methyl blue solution and flux is respectively 91.1% and 58.6L/m2h bar。
Embodiment 8
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.01g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out drying, and being subsequently placed in ammonia hydroxide/methanol mixed solution, (30%) volume ratio 100:1, the concentration of ammonium hydroxide used are Middle crystallization nucleation 12h, subsequent degassifying using vacuum 30min, final washing, drying.When operating pressure is 0.1MPa, to aqueous phase system The rejection and flux of 0.1g/L methyl blue solution are respectively 99.8% and 10.8L/m2h bar。
Embodiment 9
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.01g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out drying, and being subsequently placed in ammonia hydroxide/methanol mixed solution, (30%) volume ratio 100:1, the concentration of ammonium hydroxide used are Middle crystallization nucleation 12h, subsequent degassifying using vacuum 30min, final washing, drying.When operating pressure is 0.1MPa, hydrogen infiltration is logical Amount and its hydrogen/nitrogen ideal selectivity are respectively 106GPU and 7.6.
Embodiment 10
Use commercialization perforated membrane for alumina material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.01g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 25mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out drying, and being subsequently placed in ammonia hydroxide/methanol mixed solution, (30%) volume ratio 100:1, the concentration of ammonium hydroxide used are Middle crystallization nucleation 12h, subsequent degassifying using vacuum 30min, final washing, drying.When operating pressure is 0.1MPa, to aqueous phase system The rejection and flux of 0.1g/L methyl blue solution are respectively 98.7% and 31.9L/m2h bar。
Embodiment 11
Use commercialization perforated membrane for zirconia material, form is tubular ultra-filtration membrane, and membrane aperture is 0.1 μm, and membrane area is 10cm2, selected GO dispersing agent is deionized water, and GO dispersion liquid concentration is 0.003g/L.
The preparation method of ZIF-8@f-GO hybridized film
(1) pellumina of a length of 5cm or so is rinsed pretreatment with deionized water, remove its surface organic matter, Then inorganic matter and microorganism are put in 50 DEG C of baking ovens and dry；
(2) in deionized water by the dispersion of a certain amount of GO powder, in the way of ultrasound centrifugation, configuration concentration ratio is The GO dispersion liquid of 0.01g/L；
(3) it by the GO dispersion liquid of (2) configuration aluminium oxide basement membrane that is assembled into that treated by way of filtering deposition, takes out Filtering pressure power is 0.1MPa, and the suction filtration time is 3min；
(4) the hygrometric state GO composite membrane prepared in (3) is directly introduced in freeze drying box, temperature is -50 DEG C, ice crystal Time is 3h；It is dry 10h (1Pa) then to carry out Decompression Sublimation, final take out is put into 50 DEG C of baking ovens dry 12h；
(5) ZIF-8 presoma methanol solution is configured, wherein 2-methylimidazole concentration is 1mol/L, and zinc nitrate hexahydrate is dense Degree is 0.25mol/L；
(6) the ZIF-8 presoma methanol solution for being configured f-GO film immersion obtained in step (4) in step (5) Middle 12h takes out drying, and being subsequently placed in ammonia hydroxide/methanol mixed solution, (30%) volume ratio 100:1, the concentration of ammonium hydroxide used are Middle crystallization nucleation 12h, subsequent degassifying using vacuum 30min, final washing, drying.When operating pressure is 0.1MPa, to aqueous phase system The rejection and flux of 0.1g/L methyl blue solution are respectively 99.8% and 49.6.8L/m2h bar。

Claims (10)

1. cooperateing with building with the ZIF-8@of controllable split tunnel structure with in-situ hybridization growth pathway using Freeze Drying Technique Graphene oxide hydridization, that is, ZIF-8@f-GO seperation film method, which comprises the following steps:
(1) porous basement membrane is pre-processed, removes its surface organic matter, inorganic matter and microorganism；
(2) in deionized water by the dispersion of GO powder, in the way of ultrasound centrifugation, GO dispersion liquid is configured；
(3) by way of filtering deposition, GO is assembled to porous membrane surface, prepares the GO film of hygrometric state；
(4) the resulting hygrometric state GO composite membrane of step (3) is prepared to the GO composite membrane (f- of open structure using Freeze Drying Technique GO)；
(5) zinc nitrate hexahydrate and 2-methylimidazole are configured into ZIF-8 precursor solution according to certain mol proportion example；
(6) by the precursor solution prepared in (5) in the GO composite membrane (f-GO) of step (4) resulting open structure and surface It is filled, then the nucleation and crystallization in lye, constructs ZIF-8@graphene oxide (ZIF-8@f-GO) hybridized film.
2. according to the method for claim 1, which is characterized in that prepare GO nanofiltration membrane substrate be business tubular membrane or The inorganic porous membrane of plate membrane, membrane material are aluminium oxide, silica, zirconium oxide, and the porous membrane aperture is 0.1~1.0 μ m。
3. according to the method for claim 1, which is characterized in that the GO dispersion liquid mass percent concentration of assembling is 0.001 ~0.5%.
4. according to the method for claim 1, which is characterized in that the middle filling mode in step (6) is static dipping, filters Deposition, vacuum outgas.
5. according to the method for claim 1, which is characterized in that when step (6) is using the method deposited, step (3), step (6) pressure limit for filtering deposition is 0.01~0.1MPa, and deposition time ranges are 0.1~10min.
6. according to the method for claim 1, which is characterized in that the cryogenic temperature in step (4) is -10~-50 DEG C, ice crystal The change time is 0.5~3h；The pressure 1-10Pa of Decompression Sublimation, lyophilization time are 1~10h.
7. according to the method for claim 1, which is characterized in that in step (5) in ZIF-8 presoma each substance it is mole dense It is 10~0.1 that degree, which is 0.1~10mol/L, two kinds of monomer mole ratios,.
8. according to the method for claim 1, which is characterized in that lye nucleating agent is ammonium hydroxide and methanol mixed solution, ammonium hydroxide Volume ratio with methanol is 100~0, and the concentration of ammonium hydroxide is 30wt%.
9. the ZIF-8@f-GO seperation film being prepared according to the described in any item methods of claim 1-8.
10. being used respectively according to the purposes for the ZIF-8@f-GO seperation film that the described in any item methods of claim 1-8 are prepared Dyestuff, high price salt are separated by filtration in water, in organic phase as small molecule be separated by filtration and gas separation.
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CN109701468A (en) * 2019-01-24 2019-05-03 四川大学 The percdation of composite function nano material-synthesis building method
CN110052184A (en) * 2019-04-16 2019-07-26 暨南大学 A kind of method that gas-liquid interface prepares MOF film
CN110052184B (en) * 2019-04-16 2021-11-23 暨南大学 Method for preparing MOF (Metal organic framework) membrane at gas-liquid interface
CN112342693A (en) * 2020-10-30 2021-02-09 西安交通大学苏州研究院 Synthesis method of metal organic framework compound flexible film with limited growth
CN112342693B (en) * 2020-10-30 2022-04-15 西安交通大学苏州研究院 Synthesis method of metal organic framework compound flexible film with limited growth
CN112934007A (en) * 2021-02-22 2021-06-11 浙江大学 Method for preparing ZIF-8/GO composite gas separation membrane by converting ZIF-8 precursor
CN113144922A (en) * 2021-03-31 2021-07-23 大连理工大学 Coaxial cable type graphene oxide-zeolite molecular sieve @ hollow fiber composite membrane and preparation method thereof
CN113230907A (en) * 2021-05-17 2021-08-10 宁夏大学 Method for preparing LTL type molecular sieve membrane by space limited steam conversion method
CN113230907B (en) * 2021-05-17 2023-04-28 宁夏大学 Method for preparing LTL type molecular sieve membrane by space-limited steam conversion method
CN114288866A (en) * 2021-11-18 2022-04-08 兰州大学 Method for efficiently and rapidly preparing two-dimensional vertical heterojunction separation membrane
CN114288866B (en) * 2021-11-18 2023-09-26 兰州大学 Method for preparing two-dimensional vertical heterojunction separation membrane
CN115430428A (en) * 2022-10-11 2022-12-06 中建生态环境集团有限公司 Biochar supported iron cluster catalyst and preparation method thereof

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